US3890113A - Production of methane - Google Patents
Production of methane Download PDFInfo
- Publication number
- US3890113A US3890113A US373533A US37353373A US3890113A US 3890113 A US3890113 A US 3890113A US 373533 A US373533 A US 373533A US 37353373 A US37353373 A US 37353373A US 3890113 A US3890113 A US 3890113A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 306
- 238000000034 method Methods 0.000 claims abstract description 90
- 230000008569 process Effects 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 239000000446 fuel Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 14
- 230000000153 supplemental effect Effects 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 7
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010742 number 1 fuel oil Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003209 petroleum derivative Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000003079 shale oil Substances 0.000 claims description 3
- 239000011275 tar sand Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- -1 naphtha Substances 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000002737 fuel gas Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 238000010924 continuous production Methods 0.000 abstract description 4
- 239000008246 gaseous mixture Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000005201 scrubbing Methods 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002918 waste heat Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 235000020030 perry Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002642 NiO-MgO Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WVYYHSKIGBEZCQ-UHFFFAOYSA-N [O-2].[O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[O-2].[Cr+3].[Fe+2] WVYYHSKIGBEZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/466—Entrained flow processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/485—Entrained flow gasifiers
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/74—Construction of shells or jackets
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/78—High-pressure apparatus
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/0445—Selective methanation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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Definitions
- PRODUCTllON or METHANE [75] Inventors: Edward '11 Child, Hacienda Heights;
- a gaseous stream comprising H and (0 produced by the partial oxidation of a hydrocarbonaceous fuel is subjected to water gas shift reaction to produce a gaseous stream rich in H and CO Acid gases i.e. CO and H 8 are separately removed leaving a hydrogen-rich gas stream. At least a portion of the CO previously recovered is recombined with the hydrogen-rich stream to produce a gaseous mixture having a mole ratio H /CO of about 4 to 10.
- This gas mixture is subjected to conventional catalytic methanation to produce a fuel gas comprising in mole (dry basis) 1-1 45 to 1, and CH, 50 to 99.
- substantially pure methane may be produced by adding a second portion of CO to the aforesaid fuel gas to produce a gaseous mixture having a mole ratio H /CO of about 4, subjecting said gas mixture to conventional catalytic methanation to produce CH and H 0, and separating 1-1 0 from the process gas stream to produce substantially pure methane.
- the normally vigorous exothermic methanation reaction may be controlled better by the stepwise addition of CO to react with the hydrogen in the process gas stream.
- This invention pertains to a process for producing a gaseous stream comprising about 50-97 mole methane (dry basis), or more.
- a hydrocarbonaceous feedstock is subjected to partial oxidation with a freeoxygen containing gas comprising from about 90 to 99.9 mole O and optionally with a temperature moderator.
- the partial oxidation reaction takes place in a free-flow noncatalytic refractory lined synthesis gas generator at an autogenous temperature in the range of about 1,200 to 3,500F. and a pressure in the range of about 1 to 350 atmospheres.
- the effluent gas stream from the gas generator principally comprises CO, H CO and H and optionally contains particulate carbon, CH H 8 and COS.
- the raw process gas stream from the gas generator is cooled, cleaned and mixed with supplemental H O to produce a feed gas for water-gas shift conversion having a mole ratio H O/CO in the range of about 2 to 8. At least 75 mole of the CO is reacted with H O by catalytic water-gas shift reaction to produce H and CO After cooling, a stream of Co -rich gas is removed from the process gas stream and optionally a separate stream of H 8 and CO8 thereby producing a hydrogen-rich gas stream.
- H and substantially all of the carbon oxides in a process gas stream comprising said hydrogen-rich gas stream in admixture with at least a portion of said separated stream of CO -rich gas react to product a process gas stream substantially comprising CH H and H 0.
- the process gas stream is cooled to separate out the H 0, producing a process gas stream comprising in mole 7o; CI-I 50 to 99, and H 45 to l.
- another portion of said separated CO -rich gas stream is added to said fuel gas stream in an amount sufficient to react with substantially all of the residual hydrogen in a second catalytic methanation zone to produce a gas stream substantially comprising CH and H 0. Water is then removed from this gas stream by cooling, producing a stream of substantially pure CH i.e. about 97 mole 7a, or more.
- the present invention involves an improved continu ous process for the production of a gaseous stream comprising 50 to 97 mole CH (dry basis) or more from a hydrocarbonaceous fuel.
- a particular advantage of the subject process is that it employs as feedstock readily available, comparatively low cost, hydrocarbonaceous materials e.g., liquid and solid fuels which may contain a comparatively high content of ash and sulfur.
- the product gas has a heating value in the range of about 700 to 1005 British Thermal Unit per standard cubic foot (BTU/SCF), depending upon the methane content. It may be used as a substitute for natural gas or in organic chemical synthesis when the methane content is greater than 95 mole For example, methanol or formaldehyde may be made by the direct oxidation of methane.
- a continuous stream of process gas is produced in the reaction zone of a separate free-flow unpacked noncatalytic partial oxidation gas generator.
- the gas generator is preferably a refractory lined vertical steel pressure vessel, such as described in coassigned US. Pat. No. 3,639,261 W. L. Slater.
- a wide range of combustible carbon containing organic hydrocarbonaceous materials may be introduced into the reaction zone of the gas generator by way of a burner to be further described.
- the hydrocarbonaceous fuel is reacted in the gas generator with a freeoxygen gas containing from to 99.9 mole O
- a temperature-moderating gas may be present.
- hydrocarbonaceous as used here to describe various suitable feedstocks is intended to include gaseous, liquid, and solid hydrocarbons, carbonaceous materials, and mixtures thereof. In fact, substantially any combustible carbon containing organic material, or slurries thereof, may be included within the definition of the term hydrocarbonaceous.
- solid carbonaceous fuels such as coal, particulate carbon, petroleum coke, concentrated sewer sludge, and mixtures thereof
- gassolid suspensions such as finely ground solid carbonaceous fuels dispersed in either a temperaturemoderating gas or in a gaseous hydrocarbon
- gas-liquid-solid dispersions such as atomized liquid hydrocarbon fuel or water and particulate carbon dispersed in a temperature-moderating gas.
- the hydrocarbonaceous fuel may have a sulfur content in the range of about 0 to 10 weight percent and an ash content in the range of about 0 to 15 weight percent.
- Liquid hydrocarbon fuels are the preferred feedstocks.
- the term liquid hydrocarbon or liquid hydrocarbon fuel, as used herein to describe suitable liquid feedstocks is intended to include various materials such as liquefied petroleum gas, petroleum distillates and residues. gasoline. naphtha. kerosine. crude petroleum. asphalt. gas oil. residual oil, tar-sand and shale oil. coal oil. aromatic hydrocarbons (such as benzene, toluene. xylene fractions), coal tar. cycle gas oil from fluid-catalytic-cracking operations. furfural extract of coker gas oil. and mixtures thereof.
- Gaseous hydrocarbon fuels, as used herein to describe suitable gaseous feedstocks include ethane, propane. butane.
- pentane refinery gas.
- acetylene tail gas ethylene off-gas.
- Both gaseous and liquid feeds may be mixed and used simultaneously and may include paraffinic. olefinic. naphthenic. aromatic compounds in any proportion, and the waste products thereof.
- oxygenated hydrocarbonaceous organic materials including carbohydrates. cellulosic materials, alkehydes, organic acids, alcohols, ketones, oxygenated fuel oil. waste liquids and by-products from chemical processes containing oxygenated hydrocarbonaceous organic materials and mixtures thereof.
- the hydrocarbonaceous feed may be at room temperature; or it may be preheated to a temperature up to as high as about 600 to 1,200F., but preferably below its cracking temperature.
- the hydrocarbonaceous feed may be introduced into the burner in liquid phase or in a vaporized mixture with a temperature moderator.
- Suitable temperature moderators include H O, CO a portion of cooled clean process gas, and mixtures of the aforesaid temperature moderators.
- a temperature moderator to moderate the temperature in the reaction zone is optional and depends in general on the carbon to hydrogen ratio of the feedstock and the oxygen content of the oxidant stream.
- a temperature moderator may not be required with some gaseous hydrocarbon fuels; however, generally one is used with liquid hydrocarbon fuels.
- CO/H of the effluent product stream may be increased.
- the temperature moderator may be introduced in admixture with either or both reactant streams. Alternatively, the temperature moderator may be introduced into the reaction zone of the gas generator by itself via a separate conduit in the fuel burner.
- H O When H O is charged to the reaction zone, it may be in liquid or gaseous phase. It may be in the form of steam or water droplets. Further, the H may be mixed either with the hydrocarbonaceous feedstock or with the free-oxygen containing gas, or with both. For example, a portion of the steam may be intermixed with oxygen in an amount less than about weight percent of the oxygen and any remainder mixed with hydrocarbonaceous materials.
- the H O may be at a temperature in the range of ambient to l,0OOF.. or more.
- the weight ratio of water to hydrocarbonaceous feed may be in the range of about 0.0 to 5.0 with liquid hydrocarbon fuels, preferably about 3.0 to 5.0 lbs. of H 0 are charged per lb. of hydrocarbonaceous feed.
- free-oxygen containing gas or gaseous oxidant as used herein is intended to mean on a dry basis, from about 90 to 99.9 mole O 0 to 9.9 mole N and less than 0.1 mole rare gases.
- the free-oxygen containing gas may be passed through the burner at a temperature in the range of about ambient to l.800F.
- the ratio of free-oxygen in the gaseous oxidant to carbon in the feedstock (O/C. atom/atom) is in the range of about 0.6 to 1.5. suitably about 0.7 to 1.2, and preferably below 1.0.
- the fecdstreams are introduced into the reaction zone of the fuel gas generator by means of a fuel burner.
- a fuel burner Suitably. an annulus-type burner. such as described in coassigned U.S. Pat. No. 2,928,460 issued to duBois Eastman et al.. may be employed.
- the feedstreams are reacted by partial oxidation without a catalyst in the reaction zone of a free-flow gas generator at an autogenous temperature in the range of about l,200 to 3,500F. and at a pressure in the range of about l to 350 atmospheres absolute (atm. abs.).
- the reaction temperature is in the range of about 1,500 to 2,000F.
- the reaction pressure is preferably in the range of about 25 to 95 atm. abs.
- the reaction'time in the fuel gas generator is about 1 to 10 seconds.
- the mixture of effluent process gas leaving the gas generator may have the following dry gas composition in mole CO 9 to 50. H 26 to 48, CO 38 to 4. N 0 to 5. CH
- Unreacted particulate carbon (on the basis of carbon in the feed by weight) is about 0.2 to 20 weight percent from liquid and solid fuels and is usually negligible from gaseous hydrocarbon feeds.
- the gas generator should be operated as follows: autogenous reaction temperature-l ,200 to 1,700F., pressure-1 to 350 atmosphere, atomic ratio of free oxygen to carbon about 0.60 to 1.2, and weight ratio steam to fuel-3-5 to 1.
- While the remaining steps in the process may be conducted at various pressures in the range of about 1 to 350 atm. abs., preferably all of the remaining steps are conducted at the same pressure as that in the gas generator less ordinary drop in the line.
- Any ash or slag in the hydrocarbonaceous fuel may be separated from the effluent gas stream leaving the gas generator in a suitable gas-solids separating zone.
- a vertical slag chamber with a side outlet for the gas stream may be connected in axial alignment with the free-flow gas generator. Ash and other solids in the gas stream discharging from the lower part of reaction chamber may drop directly into a pool of water at the bottom of the slag chamber where it may be periodically removed.
- a typical arrangement for this is shown in coassigned U.S. Pat. 3,639,261.
- At least mole of the CO in the effluent gas stream from the gas generator is reacted with H O to produce CO and H by the catalytic water-gas shift reaction.
- the CO in the process gas stream may be reacted with the H therein to produce methane by the catalytic methanation reaction.
- the effluent gas stream from the gas generator is cooled to a temperature in the range of about 600 to 750F.
- this cooling may be effected by direct contact with water in a quench tank. thereby simultaneously cleaning the process gas stream and vaporizing supplemental H O into the process gas stream.
- a raw syngas stream may be produced containing more than the minimum amount of water required for a subsequent water-gas shift reaction.
- the effluent gas stream from the quench tank would contain 7 moles of H 0 per mole of CO in the gas.
- a conventional quench tank is shown in coassigned U.S. Pat. No. 2,896,927.
- scrubbing column may be carried out in scrubbing column. to be further described.
- the effluent gas stream may be cooled by indirect heat exchange with water in a waste-heat boiler, thereby producing steam at a temperature in the range of about 450 to 700F. for use elsewhere in the process.
- a suitable arrange ment utilizing a waste-heat boiler is shown in coassigned U.S. Pat. No. 3,709,669.
- the stream of process gas leaving the waste heat boiler may be passed into a gas cleaning zone where particulate carbon and any other remaining entrained solids may be removed. Contamination of the water-gas shift and methanation catalysts is thereby prevented.
- a slurry of particulate carbon in a liquid hydrocarbon fuel may be produced in the gas cleaning zone.
- this slurry may be then recycled to the gas generator as at least a portion of the feedstock.
- Any conventional procedure suitable for removing suspended solids from a gas stream may be used.
- the stream of fuel gas is introduced into a gasliquid scrubbing zone where it is scrubbed with a scrubbing fluid such as a liquid hydrocarbon or water.
- a suitable liquid-gas tray-type column is more fully described in Perry's Chemical Engineers Handbook, Fourth Edition, McGraw-Hill 1963, Pages 18-3 to 5.
- the particulate carbon may be removed from the process gas stream.
- a slurry of particulate carbon and scrubbing fluid is removed from the bottom of the column and sent to a carbon separation or concentration zone. This may be done by any conventional means that may be suitable e.g., filtration, centrifuge, gravity settling, or by liquid hydrocarbon extraction such as the process described in coassigned U.S. Pat. No. 2,992,906.
- Clean scrubbing fluid or dilute mixtures of scrubbing fluid and particulate carbon may be recycled to the top of the column for scrubbing more fuel g
- Other suitable conventional gas cooling and cleaning procedures may be used in combination with or in place of the aforesaid scrubbing column.
- the partially cooled process gas stream may be introduced below the surface of a pool of quenching and scrubbing fluid by means ofa dip-tube unit.
- the process gas stream may be passed through a plurality of scrubbing steps including the orifice-type scrubber or venturi or nozzle scrubber, such as shown in Perrys Chemical Engineers Handbook, Fourth Edition, McGraw-Hill 1963, Pages l8-54 to 56 and coassigned U.S. Pat. No. 3,639,261.
- the aforesaid gas scrubbing step may not be necessary with gaseous hydrocarbon fuels that produce substantially no particulate carbon.
- the effluent gas stream from the gas generator which has been cooled and cleaned, as previously described, and which contains supplemental H O to provide a mole ratio H O/CO in the range of about 2 to 8, and preferably 3 to 4 is reacted in a conventional water-gas shift converter.
- the shift converter may be of a fixed bed or fluidized design and contains a conventional sulfur resistant water-gas shift catalyst.
- a typical sulfur resistant shift catalyst comprises 95% Fe O and 4% CIgOg-
- the space velocity may range from 500 to 50,000 standard cubic feet of gas per cubic feet of catalyst per hour (SCF/CF hr). For example.
- a CO conversion of 92% with the aforesaid iron oxide-chromium oxide catalyst may be achieved with a feed gas comprising 35 mole 7: CO at a temperature of 842F. and a pressure of 365 psia, a space velocity of about 1,000 SCF/CF hr", and a steam: CO mole ratio of 5.7.
- At least mole 7c of the CO in the feed gas to the water-gas shift converter is converted into H and C0
- the effluent gas stream from the water-gas shift converter is cooled in a waste heat boiler from a temperature in the range of about 750 to 950F. to a tempera ture in the range of about 275 to 570F.
- the steam produced may be used where needed elsewhere in the process.
- the effluent gas stream from the water gas shift converter after removing any excess water may have the following dry gas composition in mole 7r: H 30 to 62, CO 43 to 27, CH, 0.5 to 26. CO 0.5 to 9, A N 0.1 to 4, H 8 0 to 1.8, and COS 0 to 0.1.
- CO H- S, COS, H O, NH and other gaseous impurities may be removed from the cooled and cleaned process gas stream leaving the water-gas shift conversion zone.
- Suitable conventional processes may be used involving refrigeration and physical or chemical absorption with solvents, such as methanol, n-methylpyrrolidone, triethanolamine, propylene carbonate, or alternately with amines or hot potassium carbonate or methanol.
- Excessive catalyst-bed temperatures may be prevented by distributing the Co -rich gas stream separately or in admixture with the hydrogen-rich gas stream throughout fixed or fluidized bed reactors by means of separate inlet points.
- a second portion of the CO -rich gas stream may be recycled to the fuel gas generator for use as all or a portion of the temperature-moderating gas.
- small amounts of H 8 and COS may be contained in the CO stream.
- the H 5 and COS containing solvent may be regenerated by flashing and stripping with nitrogen, or alternatively be heating and refluxing at reduced pressure without using an inert gas.
- the H 8 and COS are then converted into sulfur by a suitable process.
- the Claus process may be used for producing elemental sulfur from H S as described in Kirk-Othmcr Encyclopedia of Chemical Technology. Second Edition Volumn l9, John Wiley, 1969, Page 353. Excess S may be removed and discarded in chemical combination with limestone. or by means of a suitable commercial extraction process.
- composition of the clean and dry hydrogen-rich process gas leaving the acid-gas removal Zone in mole percent is about:
- H 52 to 93 (O 0.5 to l2, CH, 44 to 1, C0 0 to 6, A 0.2 to 0.4, and N 0 to 7.
- the temperature is in the range of about 60F. to 180F. and preferably about 70F. to l00F.
- the pressure is in the range of about 1 to 350 atm. abs. and preferably 25 to 95 atm. abs, and most preferably at a pressure substantially the same as that produced in the fuel gas generator less ordinary line drop.
- At least a portion of the CO -rich stream recovered from the acid-gas removal zone is recombined with the hydrogen-rich process gas stream from the acid-gas removal zone to provide a feed gas to the methanation zone, as previously mentioned.
- the methanation reaction may be done in one or more stages e.g. l to 3. Each stage may consist of one or more beds of catalyst with provision for cooling between each bed but preferably without any water or C0,; removed between beds. A provision to remove condensed water and to add CO is preferably provided between each stage.
- the mole ratio (H /CO of the process gas stream reacting in the methanation zone at a temperature in the range of about 400 to l,500F. may be in the range of about 4 to 10, so as to produce an effluent gas stream after the first methanation stage comprising the following dry gas composition in mole 7:: CH, 50 to 96, H 3 to 46, CO 0 to 0.5, CO 0.3 to 0.7, and A+N 0.2 to 8.
- substantially all of the carbon oxides in the process gas stream may be converted by this methanation stage into CH and H 0.
- the feed gas stream to the methanator may be preheated by indirect heat exchange with the effluent gas stream from the methanator.
- a two stage methanation zone as the reacting gas stream passes between the first and second catalyst stages, it may be cooled, dried, and mixed with a second portion of said CO -rich gas stream.
- a two-stage methanator may consist of a single catalyst bed in stage I followed by one or more catalyst beds in stage 2.
- the mole ratio (H /CO of the process gas stream reacting in the first methanator is preferably greater than 4 so as to provide an excess of hydrogen.
- substantially all of the remaining hydrogen in the process stream may be reacted with supplemental CO which is supplied by the addition of said second portion of CO rich gas stream to produce about 97 mole CH or more (dry basis).
- supplemental CO which is supplied by the addition of said second portion of CO rich gas stream to produce about 97 mole CH or more (dry basis).
- the aforesaid second portion of CO rich gas stream is supplied to the second methanator in an amount so as to provide therein a mole ratio (H /CO of about 4 i.e., preferably stoichiometric quantities.
- the sensible heat in the effluent gas stream may be recovered by indirect heat exchange with feed gas to the methanation zone as previously disclosed, or by producing steam in a waste heat boiler. Water is separated and removed during this cooling as well as at other points in the system where the gases are cooled below the dew point.
- the product gas substantially comprises CH i.e. about 97 mole 7( or more.
- portions of effluent gas streams from eithcr or both methanators may be recycled through their respective catalyst beds at ratios ranging from 150 volumes of recycle gas per volume of fresh feed gas and preferably at recycle ratios in the range of about I to 5.
- additional temperature control may be effected and the concentrations of methane in the effluent gas streams and the space velocity may be increased.
- Any conventional methanation catalyst may be employed in the subject process. This is especially true since H S and any other gaseous sulfur compounds may be removed from the process gas stream in the acid-gas removal zone as previously described.
- the group VIII transition elements mainly iron, nickel, and cobalt, appear to be the most suitable for use as methanation catalysts.
- Typical commercial preparations contain about 33 to 78 weight percent of nickel oxide and about 12 to 67 percent of aluminum oxide and are used in the form of X inch or A X inch cylindrical tablets.
- a typical nickel oxide catalyst is Girdler G65 produced by Chemetron Corp.
- Suitable catalyst compositions include the following: NiO- A1 0 or NiO-MgO precipitated on kaolin'and reduced with hydrogen; and also in parts by weight Ni 100, ThO 6, MgO l2 and Kieselguhr (diatomaceous earth) 400 reduced with hydrogen for 2 hours at 752F. followed by heating for 100 hours at 932F.
- the life of a sulfur sensitive catalyst may be extended by maintaining the sulfur level in the reactant gases below about 0.005 grains of sulfur per thousand standard cubic feet. Steam may be added to the reactant gas to decrease the amount of carbon that is deposited; however, in such instance there may be a decrease in methane yield.
- a suitable operating temperature in the methanator is in the range of about 390 to 1500F.
- the preferable exit temperature for the aforesaid NiO-Al- 0 catalyst is about 662F.
- Space velocities range from 100 to 10,000 standard volumes of gas per volume of catalyst (hr") and pressures range from 1 to 350 atmospheres.
- EXAMPLE The following example illustrates a preferred embodiment of the process of this invention. While a preferred mode of operation is illustrated, the example should not be construed as limiting the scope of the invention.
- the process is continuous and the flow rates are specified on an hourly basis.
- 1,000,000 standard cubic feet (SCF) of a raw process gas stream is produced by the partial oxidation of a hy drocarbonaceous fuel, to be further described, with oxygen in a conventional vertical noncatalytic free-flow refractory-lined gas generator.
- the raw process gas stream is produced at an autogenous temperature of about 1700F. and at a pressure of about 60 atm. abs.
- the average residence time in the gas generator is about seconds.
- the effluent gas leaving the generator has the composition shown in Table I column 1. About 800 pounds of unconverted particulate carbon are entrained in the effluent stream of process gas. All of the gas analyses shown in Table l are on a dry basis. Water is removed from the system at several points wherethe gases are cooled to a temperature below the dew point.
- the aforesaid process gas stream is produced by continuously introducing into a partial oxidation fuel gas generator by way of an annulus type burner the following charge: 28,300 pounds of reduced crude oil having the ultimate analysis (Wt/72) C 85.9, H 11.31, S 2.01, N 0.7, and ash 0.04. Further, the reduced crude oil has an API gravity of 12.9", a gross heating value of 18,200 BTU/1b, and a viscosity of 822 Saybolt Seconds Furol at 122F. Also, 390,000 SCF of substantially pure oxygen (95 mole 0 or more) at a temperature of 600F. are simultaneously introduced into the reaction zone of the gas generator by way of said burner.
- the hot effluent gas stream leaving the gas generator is passed directly into water in a conventional quench tank as shown in coassigned US. Pat. No. 2,818,326.
- the stream of effluent gas is cooled and simultaneously, steam is produced.
- Substantially all of the particulate carbon in the process gas stream is removed as a water slurry in the quench tank. Any remaining solids may be removed from the process gas stream in a conventional gas-liquid scrubbing column.
- a slurry of particulate carbon and crude oil may be produced from the carbon-water slurry and introduced into the gas generator as a portion of the feedstock.
- the effluent gas stream leaves the shift converter at a temperature of about 800F. and is cooled to a temperature of 275F. by indirect heat exchange with water in a waste heat boiler, thereby producing steam.
- the process gas stream is then introduced into a conventional acid-gas removal zone, as previously described. Substantially all of the CO H 5 and H 0 are removed from the stream of process gas and a stream of acid gas-free process gas is produced having the composition shown in Table 1 column 3.
- a feed gas mixture having a mole ratio (lb/CO of about 8.8 is produced having the composition shown in Table 1 column 4.
- This feed gas at a temperature of about 400F. and a pressure of about 60 atm. abs. is introduced into a first conventional adiabatic fixed bed methanator containing a single bed of typical nickel oxide methanation catalyst as previously described.
- the space velocity is 4000 SCF of gas per CF of catalyst (hr
- the effluent gas stream departing from the first methanator at a temperature of about 1240F. has the composition shown in Table 1 column 5.
- the process gas stream is then cooled in a waste heat boiler and mixed with 7*,000 lbs. of CO; from the CO stream produced in the said acid gas removal zone.
- a feed gas mixture to a second adiabatic catalytic methanator having a mole ratio (H /CO of about 4 as shown in Table 1 column 6 is produced.
- the second methanator and the catalyst therein are similar to the first methanator and catalyst except that at least two catalyst beds with cooling between beds are used to obtain the higher conversion to C11,.
- the aforesaid feed gas mixture is introduced at a temperature of about 400F. and a pressure of about 60 atm. abs.
- the space velocity is 4000 SCF of gas per CF of catalyst per hour.
- substantially all of the H and CO are reacted together to produce CH and H 0.
- the effluent gas leaves the second methanator at a temperature of about 620F. It is cooled to a temperature of about F. to condense out substantially all of the H 0.
- the product stream has the composition shown in Table 1 column 7.
- a process for producing a methane-rich gas stream comprising 1. producing a raw process gas stream principally comprising CO, H CO and H and optionally containing particulate carbon, CH H and COS by the partial oxidation of a hydrocarbonaceous feedstock with a free-oxygen containing gas comprising about 90 to 99.9 mole O and optionally with a temperature moderator, in the reaction zone of a gas generator at an autogenous temperature in the range of about l200 to 3500F. and a pressure in the range of about I to 350 atm. abs.;
- hydrocarbonaceous fuel is a liquid hydrocarbon selected from the group consisting of liquefied petroleum gas; petroleum distillates and residues, gasoline, naphtha, kerosine, crude petroleum asphalt, gas oil, residual oil, tar-sand oil, shale oil, coal oil; aromatic hydrocarbons such as benzene, toluene, xylene fractions, coal tar, cycle gas oil from fluid-catalytic-cracking operation; furfural extract of coker gas oil; and mixtures thereof.
- hydrocarbonaceous fuel is a gaseous hydrocarbon selected from the group consisting of ethane, propane, butane, pentane, refinery gas, acetylene tail gas, ethylene off-gas, and mixtures thereof.
- a process for producing a gaseous stream comprising about 97 mole methane or more comprising 1. producing a raw process gas stream principally comprising CO, H CO and H 0, and optionally containing particulate carbon, CH H 8 and COS by partial oxidation of a hydrocarbonaceous feedstock with a free-oxygen containing gas comprising about to 99.9 mole O and optionally with a temperature moderator, in the reaction zone of a free-flow noncatalytic gas generator at an autogenous temperature in the range of about l200 to 3500F. and a pressure in the range of about 1 to 350 atm. abs.;
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Abstract
Continuous process for the production of a gaseous stream comprising about 50 to 97 mole % methane (dry basis) or higher from a sulfur containing hydrocarbonaceous fuel without polluting the environment. A gaseous stream comprising H2 and CO produced by the partial oxidation of a hydrocarbonaceous fuel is subjected to water gas shift reaction to produce a gaseous stream rich in H2 and CO2. Acid gases i.e. CO2 and H2S are separately removed leaving a hydrogen-rich gas stream. At least a portion of the CO2 previously recovered is recombined with the hydrogen-rich stream to produce a gaseous mixture having a mole ratio H2/CO2 of about 4 to 10. This gas mixture is subjected to conventional catalytic methanation to produce a fuel gas comprising in mole % (dry basis) H2 45 to 1, and CH4 50 to 99. By using the reaction of CO2 and H2 rather than the reaction of CO and H2, a reduction of about 25% in the very large heat release encountered with the methanation reaction may be achieved. Optionally, substantially pure methane may be produced by adding a second portion of CO2 to the aforesaid fuel gas to produce a gaseous mixture having a mole ratio H2/CO2 of about 4, subjecting said gas mixture to conventional catalytic methanation to produce CH4 and H2O, and separating H2O from the process gas stream to produce substantially pure methane. Thus, the normally vigorous exothermic methanation reaction may be controlled better by the stepwise addition of CO2 to react with the hydrogen in the process gas stream.
Description
States atent 1191 Child et al.
[ 1 June 17, 1975 4] PRODUCTllON or METHANE [75] Inventors: Edward '11 Child, Hacienda Heights;
Allen M. Robin, Anaheim. both of Calif.
[73] Assignee: Texaco llnc., New York, NY.
{22] Filed: June 25, 1973 [21] Appl. No.: 373,533
[51] Int. Cl. C101) 49/02; C10b 57/02 [58] Field of Search 48/197 R, 202, 209-215;
[56] References Cited UNITED STATES PATENTS 2,133,496 10/1938 Winkler ct a1. 1. 48/211 2,660,521 11/1953 Teichmann l 1 48/211 X 2.662.816 12/1953 Kalbach 48/202 2,963,348 12/1960 Sellers 48/197 R X 3,069,249 12/1962 Herbert ct al 48/197 R 3,511,624 5/1970 Humphries ct a1. 48/197 R 3,531,267 9/1970 Gould l l 48/213 3,709,669 1/1973 Marion ct a1. 48/215 [57} ABSTRACT Continuous process for the production of a gaseous stream comprising about 50 to 97 mole '71 methane (dry basis) or higher from a sulfur containing hydrocarbonaceous fuel without polluting the environment.
A gaseous stream comprising H and (0 produced by the partial oxidation of a hydrocarbonaceous fuel is subjected to water gas shift reaction to produce a gaseous stream rich in H and CO Acid gases i.e. CO and H 8 are separately removed leaving a hydrogen-rich gas stream. At least a portion of the CO previously recovered is recombined with the hydrogen-rich stream to produce a gaseous mixture having a mole ratio H /CO of about 4 to 10. This gas mixture is subjected to conventional catalytic methanation to produce a fuel gas comprising in mole (dry basis) 1-1 45 to 1, and CH, 50 to 99. By using the reaction of CO and H rather than the reaction of CO and H a reduction of about 25% in the very large heat release encountered with the methanation reaction may be achieved.
Optionally, substantially pure methane may be produced by adding a second portion of CO to the aforesaid fuel gas to produce a gaseous mixture having a mole ratio H /CO of about 4, subjecting said gas mixture to conventional catalytic methanation to produce CH and H 0, and separating 1-1 0 from the process gas stream to produce substantially pure methane. Thus, the normally vigorous exothermic methanation reaction may be controlled better by the stepwise addition of CO to react with the hydrogen in the process gas stream.
10 Claims, 1 Drawing Figure 1 PRODUCTION OF METHANE BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a continuous process for the production of a gaseous stream comprising about 50 to 97 mole methane (dry basis), or more.
2. Description of the Prior Art .Fossil fuels, which took nature millions of years to create, are being consumed at such prodigious rates that available petroleum supplies may be good for only 50 more years and coal supplies for two or three more centuries. The accelerating demand for fuel has contributed to the present energy crisis. A typical natural gas contains about 94.9% methane. Since natural gas appears to be the scarcest of the fossil fuels, the development of an economical nonpolluting process for producing synthetic natural gas or substantially pure methane from sulfur containing coal and comparatively low cost petroleum crude or residual products is of considerable importance.
A large amount of heat is released during the catalytic reaction of H and CO to produce CH Accordingly, sophisticated. complex, and costly methanation systems would ordinarily be required for the methanation of gas mixtures containing a high CO H content. In the subject process, the normally vigorous exothermic methanation reaction is controlled thereby permitting the use of comparatively low cost conventional fixed bed adiabatic reactors.
SUMMARY This invention pertains to a process for producing a gaseous stream comprising about 50-97 mole methane (dry basis), or more. By using the reaction of CO and H rather than the reaction of CO and H a reduction of about 25% in the very large heat release encountered with the methanation reaction may be achieved. In the process, a hydrocarbonaceous feedstock is subjected to partial oxidation with a freeoxygen containing gas comprising from about 90 to 99.9 mole O and optionally with a temperature moderator. The partial oxidation reaction takes place in a free-flow noncatalytic refractory lined synthesis gas generator at an autogenous temperature in the range of about 1,200 to 3,500F. and a pressure in the range of about 1 to 350 atmospheres. The effluent gas stream from the gas generator principally comprises CO, H CO and H and optionally contains particulate carbon, CH H 8 and COS.
The raw process gas stream from the gas generator is cooled, cleaned and mixed with supplemental H O to produce a feed gas for water-gas shift conversion having a mole ratio H O/CO in the range of about 2 to 8. At least 75 mole of the CO is reacted with H O by catalytic water-gas shift reaction to produce H and CO After cooling, a stream of Co -rich gas is removed from the process gas stream and optionally a separate stream of H 8 and CO8 thereby producing a hydrogen-rich gas stream. In a catalytic methanation zone, H and substantially all of the carbon oxides in a process gas stream comprising said hydrogen-rich gas stream in admixture with at least a portion of said separated stream of CO -rich gas react to product a process gas stream substantially comprising CH H and H 0. The process gas stream is cooled to separate out the H 0, producing a process gas stream comprising in mole 7o; CI-I 50 to 99, and H 45 to l. Optionally, another portion of said separated CO -rich gas stream is added to said fuel gas stream in an amount sufficient to react with substantially all of the residual hydrogen in a second catalytic methanation zone to produce a gas stream substantially comprising CH and H 0. Water is then removed from this gas stream by cooling, producing a stream of substantially pure CH i.e. about 97 mole 7a, or more.
BRIEF DESCRIPTION OF THE DRAWING DESCRIPTION OF THE INVENTION The present invention involves an improved continu ous process for the production of a gaseous stream comprising 50 to 97 mole CH (dry basis) or more from a hydrocarbonaceous fuel.
A particular advantage of the subject process is that it employs as feedstock readily available, comparatively low cost, hydrocarbonaceous materials e.g., liquid and solid fuels which may contain a comparatively high content of ash and sulfur. The product gas has a heating value in the range of about 700 to 1005 British Thermal Unit per standard cubic foot (BTU/SCF), depending upon the methane content. It may be used as a substitute for natural gas or in organic chemical synthesis when the methane content is greater than 95 mole For example, methanol or formaldehyde may be made by the direct oxidation of methane.
In the subject process, first a continuous stream of process gas is produced in the reaction zone of a separate free-flow unpacked noncatalytic partial oxidation gas generator. The gas generator is preferably a refractory lined vertical steel pressure vessel, such as described in coassigned US. Pat. No. 3,639,261 W. L. Slater.
A wide range of combustible carbon containing organic hydrocarbonaceous materials may be introduced into the reaction zone of the gas generator by way of a burner to be further described. The hydrocarbonaceous fuel is reacted in the gas generator with a freeoxygen gas containing from to 99.9 mole O Optionally, a temperature-moderating gas may be present.
The term hydrocarbonaceous as used here to describe various suitable feedstocks is intended to include gaseous, liquid, and solid hydrocarbons, carbonaceous materials, and mixtures thereof. In fact, substantially any combustible carbon containing organic material, or slurries thereof, may be included within the definition of the term hydrocarbonaceous. For example, there are (l) pumpable slurries of solid carbonaceous fuels, such as coal, particulate carbon, petroleum coke, concentrated sewer sludge, and mixtures thereof; (2) gassolid suspensions, such as finely ground solid carbonaceous fuels dispersed in either a temperaturemoderating gas or in a gaseous hydrocarbon; and (3) gas-liquid-solid dispersions, such as atomized liquid hydrocarbon fuel or water and particulate carbon dispersed in a temperature-moderating gas. The hydrocarbonaceous fuel may have a sulfur content in the range of about 0 to 10 weight percent and an ash content in the range of about 0 to 15 weight percent.
Liquid hydrocarbon fuels are the preferred feedstocks. The term liquid hydrocarbon or liquid hydrocarbon fuel, as used herein to describe suitable liquid feedstocks, is intended to include various materials such as liquefied petroleum gas, petroleum distillates and residues. gasoline. naphtha. kerosine. crude petroleum. asphalt. gas oil. residual oil, tar-sand and shale oil. coal oil. aromatic hydrocarbons (such as benzene, toluene. xylene fractions), coal tar. cycle gas oil from fluid-catalytic-cracking operations. furfural extract of coker gas oil. and mixtures thereof. Gaseous hydrocarbon fuels, as used herein to describe suitable gaseous feedstocks. include ethane, propane. butane. pentane, refinery gas. acetylene tail gas, ethylene off-gas. and mixtures thereof. Both gaseous and liquid feeds may be mixed and used simultaneously and may include paraffinic. olefinic. naphthenic. aromatic compounds in any proportion, and the waste products thereof.
Also included within the definition of the term bydrocarabonaceous are oxygenated hydrocarbonaceous organic materials including carbohydrates. cellulosic materials, alkehydes, organic acids, alcohols, ketones, oxygenated fuel oil. waste liquids and by-products from chemical processes containing oxygenated hydrocarbonaceous organic materials and mixtures thereof.
The hydrocarbonaceous feed may be at room temperature; or it may be preheated to a temperature up to as high as about 600 to 1,200F., but preferably below its cracking temperature. The hydrocarbonaceous feed may be introduced into the burner in liquid phase or in a vaporized mixture with a temperature moderator. Suitable temperature moderators include H O, CO a portion of cooled clean process gas, and mixtures of the aforesaid temperature moderators.
The use of a temperature moderator to moderate the temperature in the reaction zone is optional and depends in general on the carbon to hydrogen ratio of the feedstock and the oxygen content of the oxidant stream. A temperature moderator may not be required with some gaseous hydrocarbon fuels; however, generally one is used with liquid hydrocarbon fuels. When a CO -containing gas stream such as that obtained subsequently in the process in the acid-gas separation zone. is used as the temperature moderator, the mole ratio (CO/H of the effluent product stream may be increased. As previously mentioned, the temperature moderator may be introduced in admixture with either or both reactant streams. Alternatively, the temperature moderator may be introduced into the reaction zone of the gas generator by itself via a separate conduit in the fuel burner.
When H O is charged to the reaction zone, it may be in liquid or gaseous phase. It may be in the form of steam or water droplets. Further, the H may be mixed either with the hydrocarbonaceous feedstock or with the free-oxygen containing gas, or with both. For example, a portion of the steam may be intermixed with oxygen in an amount less than about weight percent of the oxygen and any remainder mixed with hydrocarbonaceous materials. The H O may be at a temperature in the range of ambient to l,0OOF.. or more. The weight ratio of water to hydrocarbonaceous feed may be in the range of about 0.0 to 5.0 with liquid hydrocarbon fuels, preferably about 3.0 to 5.0 lbs. of H 0 are charged per lb. of hydrocarbonaceous feed.
The term free-oxygen containing gas or gaseous oxidant as used herein is intended to mean on a dry basis, from about 90 to 99.9 mole O 0 to 9.9 mole N and less than 0.1 mole rare gases. The free-oxygen containing gas may be passed through the burner at a temperature in the range of about ambient to l.800F. The ratio of free-oxygen in the gaseous oxidant to carbon in the feedstock (O/C. atom/atom) is in the range of about 0.6 to 1.5. suitably about 0.7 to 1.2, and preferably below 1.0. I
The fecdstreams are introduced into the reaction zone of the fuel gas generator by means of a fuel burner. Suitably. an annulus-type burner. such as described in coassigned U.S. Pat. No. 2,928,460 issued to duBois Eastman et al.. may be employed.
The feedstreams are reacted by partial oxidation without a catalyst in the reaction zone of a free-flow gas generator at an autogenous temperature in the range of about l,200 to 3,500F. and at a pressure in the range of about l to 350 atmospheres absolute (atm. abs.). Preferably, the reaction temperature is in the range of about 1,500 to 2,000F. and the reaction pressure is preferably in the range of about 25 to 95 atm. abs. The reaction'time in the fuel gas generator is about 1 to 10 seconds. The mixture of effluent process gas leaving the gas generator may have the following dry gas composition in mole CO 9 to 50. H 26 to 48, CO 38 to 4. N 0 to 5. CH
27 to 0.1, H 8 nil to 2.0, COS nil to 0.1, and A 0.1 to 0.2. Unreacted particulate carbon (on the basis of carbon in the feed by weight) is about 0.2 to 20 weight percent from liquid and solid fuels and is usually negligible from gaseous hydrocarbon feeds.
To produce an effluent gas stream from the gas generator containing at least 10 mole CH (dry basis) as disclosed in coassigned U.S. Pat. No. 3,688,438, the gas generator should be operated as follows: autogenous reaction temperature-l ,200 to 1,700F., pressure-1 to 350 atmosphere, atomic ratio of free oxygen to carbon about 0.60 to 1.2, and weight ratio steam to fuel-3-5 to 1.
While the remaining steps in the process may be conducted at various pressures in the range of about 1 to 350 atm. abs., preferably all of the remaining steps are conducted at the same pressure as that in the gas generator less ordinary drop in the line.
Any ash or slag in the hydrocarbonaceous fuel may be separated from the effluent gas stream leaving the gas generator in a suitable gas-solids separating zone. For example, a vertical slag chamber with a side outlet for the gas stream may be connected in axial alignment with the free-flow gas generator. Ash and other solids in the gas stream discharging from the lower part of reaction chamber may drop directly into a pool of water at the bottom of the slag chamber where it may be periodically removed. A typical arrangement for this is shown in coassigned U.S. Pat. 3,639,261.
In the subject process, at least mole of the CO in the effluent gas stream from the gas generator is reacted with H O to produce CO and H by the catalytic water-gas shift reaction. The CO in the process gas stream may be reacted with the H therein to produce methane by the catalytic methanation reaction. By this scheme in comparison with the exothermic reaction between CO and H to produce methane, advantageously there may be achieved a reduction of about 25% in the very large amount of heat released.
The effluent gas stream from the gas generator is cooled to a temperature in the range of about 600 to 750F. Preferably, this cooling may be effected by direct contact with water in a quench tank. thereby simultaneously cleaning the process gas stream and vaporizing supplemental H O into the process gas stream. By this means a raw syngas stream may be produced containing more than the minimum amount of water required for a subsequent water-gas shift reaction. For example, with a quench temperature of about 400F. the effluent gas stream from the quench tank would contain 7 moles of H 0 per mole of CO in the gas. For example, a conventional quench tank is shown in coassigned U.S. Pat. No. 2,896,927. If required, additional scrubbing may be carried out in scrubbing column. to be further described. Alternatively. the effluent gas stream may be cooled by indirect heat exchange with water in a waste-heat boiler, thereby producing steam at a temperature in the range of about 450 to 700F. for use elsewhere in the process. A suitable arrange ment utilizing a waste-heat boiler is shown in coassigned U.S. Pat. No. 3,709,669.
When indirect heat exchange is employed, the stream of process gas leaving the waste heat boiler may be passed into a gas cleaning zone where particulate carbon and any other remaining entrained solids may be removed. Contamination of the water-gas shift and methanation catalysts is thereby prevented. A slurry of particulate carbon in a liquid hydrocarbon fuel may be produced in the gas cleaning zone. Optionally, this slurry may be then recycled to the gas generator as at least a portion of the feedstock. Any conventional procedure suitable for removing suspended solids from a gas stream may be used. In one embodiment of the invention, the stream of fuel gas is introduced into a gasliquid scrubbing zone where it is scrubbed with a scrubbing fluid such as a liquid hydrocarbon or water. A suitable liquid-gas tray-type column is more fully described in Perry's Chemical Engineers Handbook, Fourth Edition, McGraw-Hill 1963, Pages 18-3 to 5.
Thus, by passing the stream of process gas up a scrubbing column in direct contact and countercurrent flow with a suitable scrubbing fluid or with dilute mixtures of particulate carbon and scrubbing fluid flowing down the column, the particulate carbon may be removed from the process gas stream. A slurry of particulate carbon and scrubbing fluid is removed from the bottom of the column and sent to a carbon separation or concentration zone. This may be done by any conventional means that may be suitable e.g., filtration, centrifuge, gravity settling, or by liquid hydrocarbon extraction such as the process described in coassigned U.S. Pat. No. 2,992,906. Clean scrubbing fluid or dilute mixtures of scrubbing fluid and particulate carbon may be recycled to the top of the column for scrubbing more fuel g Other suitable conventional gas cooling and cleaning procedures may be used in combination with or in place of the aforesaid scrubbing column. For example, the partially cooled process gas stream may be introduced below the surface of a pool of quenching and scrubbing fluid by means ofa dip-tube unit. Or the process gas stream may be passed through a plurality of scrubbing steps including the orifice-type scrubber or venturi or nozzle scrubber, such as shown in Perrys Chemical Engineers Handbook, Fourth Edition, McGraw-Hill 1963, Pages l8-54 to 56 and coassigned U.S. Pat. No. 3,639,261. The aforesaid gas scrubbing step may not be necessary with gaseous hydrocarbon fuels that produce substantially no particulate carbon.
The effluent gas stream from the gas generator which has been cooled and cleaned, as previously described, and which contains supplemental H O to provide a mole ratio H O/CO in the range of about 2 to 8, and preferably 3 to 4 is reacted in a conventional water-gas shift converter. The shift converter may be of a fixed bed or fluidized design and contains a conventional sulfur resistant water-gas shift catalyst. A typical sulfur resistant shift catalyst comprises 95% Fe O and 4% CIgOg- The space velocity may range from 500 to 50,000 standard cubic feet of gas per cubic feet of catalyst per hour (SCF/CF hr). For example. a CO conversion of 92% with the aforesaid iron oxide-chromium oxide catalyst may be achieved with a feed gas comprising 35 mole 7: CO at a temperature of 842F. and a pressure of 365 psia, a space velocity of about 1,000 SCF/CF hr", and a steam: CO mole ratio of 5.7.
At least mole 7c of the CO in the feed gas to the water-gas shift converter is converted into H and C0 The effluent gas stream from the water-gas shift converter is cooled in a waste heat boiler from a temperature in the range of about 750 to 950F. to a tempera ture in the range of about 275 to 570F. The steam produced may be used where needed elsewhere in the process. The effluent gas stream from the water gas shift converter after removing any excess water may have the following dry gas composition in mole 7r: H 30 to 62, CO 43 to 27, CH, 0.5 to 26. CO 0.5 to 9, A N 0.1 to 4, H 8 0 to 1.8, and COS 0 to 0.1.
In an acid-gas removal zone, CO H- S, COS, H O, NH and other gaseous impurities may be removed from the cooled and cleaned process gas stream leaving the water-gas shift conversion zone. Suitable conventional processes may be used involving refrigeration and physical or chemical absorption with solvents, such as methanol, n-methylpyrrolidone, triethanolamine, propylene carbonate, or alternately with amines or hot potassium carbonate or methanol.
In solvent absorption processes, most of the CO absorbed in the solvent may be released by simple flashing. The rest may be removed by stripping. This may be done most economically with nitrogen. Nitrogen is available as a low cost by-product from an air separation unit used to produce the free-oxygen containing gas used in the gas generator. The regenerated solvent is then recycled to the absorption column for reuse. When necessary, final cleanup may be accomplished by passing the process gas through iron oxide, zinc oxide, or activated carbon to remove residual traces of H 8 or organic sulfide. At least a portion of the stream of CO rich gas comprising CO in the range of about 95-99 mole and preferably more than 98.5% may be admixed with the reacting process gas stream in the methantion zone, to be further described. Excessive catalyst-bed temperatures may be prevented by distributing the Co -rich gas stream separately or in admixture with the hydrogen-rich gas stream throughout fixed or fluidized bed reactors by means of separate inlet points. A second portion of the CO -rich gas stream may be recycled to the fuel gas generator for use as all or a portion of the temperature-moderating gas. In such case, small amounts of H 8 and COS may be contained in the CO stream.
The H 5 and COS containing solvent may be regenerated by flashing and stripping with nitrogen, or alternatively be heating and refluxing at reduced pressure without using an inert gas. The H 8 and COS are then converted into sulfur by a suitable process. For example, the Claus process may be used for producing elemental sulfur from H S as described in Kirk-Othmcr Encyclopedia of Chemical Technology. Second Edition Volumn l9, John Wiley, 1969, Page 353. Excess S may be removed and discarded in chemical combination with limestone. or by means of a suitable commercial extraction process.
In general, the composition of the clean and dry hydrogen-rich process gas leaving the acid-gas removal Zone in mole percent is about:
H 52 to 93, (O 0.5 to l2, CH, 44 to 1, C0 0 to 6, A 0.2 to 0.4, and N 0 to 7. The temperature is in the range of about 60F. to 180F. and preferably about 70F. to l00F., and the pressure is in the range of about 1 to 350 atm. abs. and preferably 25 to 95 atm. abs, and most preferably at a pressure substantially the same as that produced in the fuel gas generator less ordinary line drop.
At least a portion of the CO -rich stream recovered from the acid-gas removal zone is recombined with the hydrogen-rich process gas stream from the acid-gas removal zone to provide a feed gas to the methanation zone, as previously mentioned. The methanation reaction may be done in one or more stages e.g. l to 3. Each stage may consist of one or more beds of catalyst with provision for cooling between each bed but preferably without any water or C0,; removed between beds. A provision to remove condensed water and to add CO is preferably provided between each stage. Thus, in a single stage methanation zone, which may actually consist of from about one to three beds of catalyst, the mole ratio (H /CO of the process gas stream reacting in the methanation zone at a temperature in the range of about 400 to l,500F., may be in the range of about 4 to 10, so as to produce an effluent gas stream after the first methanation stage comprising the following dry gas composition in mole 7:: CH, 50 to 96, H 3 to 46, CO 0 to 0.5, CO 0.3 to 0.7, and A+N 0.2 to 8. Note that substantially all of the carbon oxides in the process gas stream may be converted by this methanation stage into CH and H 0. Optionally, the feed gas stream to the methanator may be preheated by indirect heat exchange with the effluent gas stream from the methanator.
In a two stage methanation zone, as the reacting gas stream passes between the first and second catalyst stages, it may be cooled, dried, and mixed with a second portion of said CO -rich gas stream. For example, a two-stage methanator may consist of a single catalyst bed in stage I followed by one or more catalyst beds in stage 2. In such case, the mole ratio (H /CO of the process gas stream reacting in the first methanator is preferably greater than 4 so as to provide an excess of hydrogen. Then in the second catalyst stage at a temperature in the range of about 400 to l,lOOF., substantially all of the remaining hydrogen in the process stream may be reacted with supplemental CO which is supplied by the addition of said second portion of CO rich gas stream to produce about 97 mole CH or more (dry basis). The aforesaid second portion of CO rich gas stream is supplied to the second methanator in an amount so as to provide therein a mole ratio (H /CO of about 4 i.e., preferably stoichiometric quantities. By this means substantially all of the H and carbon dioxide in the process gas stream may be converted into CH and H 0.
The sensible heat in the effluent gas stream may be recovered by indirect heat exchange with feed gas to the methanation zone as previously disclosed, or by producing steam in a waste heat boiler. Water is separated and removed during this cooling as well as at other points in the system where the gases are cooled below the dew point. The product gas substantially comprises CH i.e. about 97 mole 7( or more.
Optionally, portions of effluent gas streams from eithcr or both methanators may be recycled through their respective catalyst beds at ratios ranging from 150 volumes of recycle gas per volume of fresh feed gas and preferably at recycle ratios in the range of about I to 5. By this means, additional temperature control may be effected and the concentrations of methane in the effluent gas streams and the space velocity may be increased.
In contrast with the subject invention, when stoichiometric quantities of CO and H are subjected to catalytic methanation in the manner disclosed in coassigned US. Pat. No. 3,709,669, special techniques and reactors may be necessary to prevent uncontrollable heat releases if upsets occur in the methanation reaction. Excessive catalyst-bed temperature may destroy the activity of the catalyst and reduce methane yields. By means of the subject invention, the maximum heat rise will be about 980F. This is within the tolerable range of commercial methanation catalysts which can operate from about 400F. inlet temperatures to l,500F. outlet temperatures.
Any conventional methanation catalyst may be employed in the subject process. This is especially true since H S and any other gaseous sulfur compounds may be removed from the process gas stream in the acid-gas removal zone as previously described.
The group VIII transition elements, mainly iron, nickel, and cobalt, appear to be the most suitable for use as methanation catalysts. Typical commercial preparations contain about 33 to 78 weight percent of nickel oxide and about 12 to 67 percent of aluminum oxide and are used in the form of X inch or A X inch cylindrical tablets. A typical nickel oxide catalyst is Girdler G65 produced by Chemetron Corp. Suitable catalyst compositions include the following: NiO- A1 0 or NiO-MgO precipitated on kaolin'and reduced with hydrogen; and also in parts by weight Ni 100, ThO 6, MgO l2 and Kieselguhr (diatomaceous earth) 400 reduced with hydrogen for 2 hours at 752F. followed by heating for 100 hours at 932F. The life of a sulfur sensitive catalyst may be extended by maintaining the sulfur level in the reactant gases below about 0.005 grains of sulfur per thousand standard cubic feet. Steam may be added to the reactant gas to decrease the amount of carbon that is deposited; however, in such instance there may be a decrease in methane yield. A suitable operating temperature in the methanator is in the range of about 390 to 1500F. For example, the preferable exit temperature for the aforesaid NiO-Al- 0 catalyst is about 662F. Space velocities range from 100 to 10,000 standard volumes of gas per volume of catalyst (hr") and pressures range from 1 to 350 atmospheres.
EXAMPLE The following example illustrates a preferred embodiment of the process of this invention. While a preferred mode of operation is illustrated, the example should not be construed as limiting the scope of the invention. The process is continuous and the flow rates are specified on an hourly basis.
1,000,000 standard cubic feet (SCF) of a raw process gas stream is produced by the partial oxidation of a hy drocarbonaceous fuel, to be further described, with oxygen in a conventional vertical noncatalytic free-flow refractory-lined gas generator. The raw process gas stream is produced at an autogenous temperature of about 1700F. and at a pressure of about 60 atm. abs. The average residence time in the gas generator is about seconds. The effluent gas leaving the generator has the composition shown in Table I column 1. About 800 pounds of unconverted particulate carbon are entrained in the effluent stream of process gas. All of the gas analyses shown in Table l are on a dry basis. Water is removed from the system at several points wherethe gases are cooled to a temperature below the dew point.
The aforesaid process gas stream is produced by continuously introducing into a partial oxidation fuel gas generator by way of an annulus type burner the following charge: 28,300 pounds of reduced crude oil having the ultimate analysis (Wt/72) C 85.9, H 11.31, S 2.01, N 0.7, and ash 0.04. Further, the reduced crude oil has an API gravity of 12.9", a gross heating value of 18,200 BTU/1b, and a viscosity of 822 Saybolt Seconds Furol at 122F. Also, 390,000 SCF of substantially pure oxygen (95 mole 0 or more) at a temperature of 600F. are simultaneously introduced into the reaction zone of the gas generator by way of said burner.
The hot effluent gas stream leaving the gas generator is passed directly into water in a conventional quench tank as shown in coassigned US. Pat. No. 2,818,326. By direct heat exchange with water in the quench tank, the stream of effluent gas is cooled and simultaneously, steam is produced. Substantially all of the particulate carbon in the process gas stream is removed as a water slurry in the quench tank. Any remaining solids may be removed from the process gas stream in a conventional gas-liquid scrubbing column. Optionally, as previously described a slurry of particulate carbon and crude oil may be produced from the carbon-water slurry and introduced into the gas generator as a portion of the feedstock.
About 19,500 pounds of supplemental H O i.e. steam as. previously produced are mixed with the cooled and cleaned effluent gas stream. The gas mixture at a temperature of 750F. and a pressure of about 60 atm. abs. is introduced into a conventional catalytic water-gas shift reactor containing sulfur resistant iron oxidechromium oxide water-gas shift catalyst Le. 95% Fe- O and 4% Cr O as previously described. The space velocity is 800 SCF of gas per CF of catalyst (hr The composition of the shifted gas is shown in Table 1 column 2. Thus, about mole 70 of the CO is converted into H and CO by the water-gas shift reaction.
The effluent gas stream leaves the shift converter at a temperature of about 800F. and is cooled to a temperature of 275F. by indirect heat exchange with water in a waste heat boiler, thereby producing steam. The process gas stream is then introduced into a conventional acid-gas removal zone, as previously described. Substantially all of the CO H 5 and H 0 are removed from the stream of process gas and a stream of acid gas-free process gas is produced having the composition shown in Table 1 column 3.
About 6,200 pounds of supplemental CO from the CO stream recovered previously in the acid gas removal zone are mixed with the clean hydrogen-rich gas stream leaving the acid gas removal zone. A feed gas mixture having a mole ratio (lb/CO of about 8.8 is produced having the composition shown in Table 1 column 4. This feed gas at a temperature of about 400F. and a pressure of about 60 atm. abs. is introduced into a first conventional adiabatic fixed bed methanator containing a single bed of typical nickel oxide methanation catalyst as previously described. The space velocity is 4000 SCF of gas per CF of catalyst (hr The effluent gas stream departing from the first methanator at a temperature of about 1240F. has the composition shown in Table 1 column 5. The process gas stream is then cooled in a waste heat boiler and mixed with 7*,000 lbs. of CO; from the CO stream produced in the said acid gas removal zone. A feed gas mixture to a second adiabatic catalytic methanator having a mole ratio (H /CO of about 4 as shown in Table 1 column 6 is produced.
The second methanator and the catalyst therein are similar to the first methanator and catalyst except that at least two catalyst beds with cooling between beds are used to obtain the higher conversion to C11,. The aforesaid feed gas mixture is introduced at a temperature of about 400F. and a pressure of about 60 atm. abs. The space velocity is 4000 SCF of gas per CF of catalyst per hour. In the second methanator, substantially all of the H and CO are reacted together to produce CH and H 0.
The effluent gas leaves the second methanator at a temperature of about 620F. It is cooled to a temperature of about F. to condense out substantially all of the H 0. The product stream has the composition shown in Table 1 column 7.
TABLE I COMPOSITION OF GAS STREAMS (DRY BASIS) Raw Process Shifted Acid Gas Free Methanator Methanator Methanator Product Gas Gas Process Gas No. 1 Feed-l-CO No. 1 Exit No. 2 Feed+CO Stream 7r MSCFH 7( MSCFH 7r MSCFH 7c MSCFH 71' MSCFH 7r- MSCFH 7r MSC FH CH, 20.49 205 18.25 205 29.75 205 27.60 205 53.18 268 48.05 268 97.15 325 CO 13.73 137 1.25 14 2.03 14 1.89 14 0.52 3 0.47 3 0.00 0 H 34.57 346 41.73 469 68.02 469 63.18 469 45.68 230 41.27 230 1.96 6 CO 30.77 308 38.38 431 0.00 0 7.15 53 0.35 2 9.97 55 0.49 2 H 5 0.30 3 0.27 3 0.00 0 0.00 0 0.00 0 0.00 0 0.00 0 A+1-l 0.14 1 0.12 1 0.20 1 0.18 l 0.27 l 0.24 l 0.40 1 100.00 1000 100.00 1123 100.00 689 100.00 742 100.00 504 100.00 557 100.00 334 This example shows how the methanation of a syngas stream to almost pure methane i.e. more than 97 mole 7! CH, having a heating value of 990 BTU/SCF has been undertaken by the use of two stages of simple fixed bed adiabatic methanators. At no point in the process was there a condition where runaway methanation could occur. If this same syngas had been methanated using the conventional procedure of reacting the H with the CO in stoichiometric proportions it would have required a very complex reactor system which is not commercially proven at this time and which could easily result in runaway reactions. Even if two separate reactor systems were used the heat release would still be too large to permit the use of fixed bed adiabatic reactors as used in the scheme proposed by this invention.
The process of the invention has been described generally and by examples with reference to hydrocarbonaceous feedstocks and scrubbing fluids of particular composition for purposes of clarity and illustration only. From the foregoing it will be apparent to those skilled in the art that various modifications of the process and the raw materials disclosed herein can be made without departure from the spirit of the invention.
We claim:
1. A process for producing a methane-rich gas stream comprising 1. producing a raw process gas stream principally comprising CO, H CO and H and optionally containing particulate carbon, CH H and COS by the partial oxidation of a hydrocarbonaceous feedstock with a free-oxygen containing gas comprising about 90 to 99.9 mole O and optionally with a temperature moderator, in the reaction zone of a gas generator at an autogenous temperature in the range of about l200 to 3500F. and a pressure in the range of about I to 350 atm. abs.;
2. cooling, cleaning and adding supplemental H O to the effluent gas stream from (1) to produce a feed gas stream for water-gas shift conversion having a mole ratio H O/CO in the range of about 2 to 8;
, 3. reacting the feed gas stream from (2) in a catalytic water-gas shift conversion zone at a temperature in the range of about 650 to 950F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole of the CO is reacted with H O to produce H and C0 4. cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO -rich gas stream and optionally a separate stream of H 8 and COS, producing a hydrogen-rich gas stream;
5. mixing at least a portion of the CO -rich gas stream from (4) with the hydrogen-rich gas stream from (4) providing a feed gas mixture having a mole ratio H /CO in the range of 4 to 10, reacting together at a temperature in the range of about 400 to l500F. in a catalytic methanation zone hydrogen and substantially all of the carbon oxides in said feed gas mixture, and removing from said methanation zone an effluent gas stream substantially comprising in mole dry basis CH, 50 to 96, H 3 to 46, CO 0 to 0.5, CO 0.3 to 0.7, A+N 0.2 to 8; and
b. cooling the effluent gas stream from (5) and separesistant catalyst comprising 95 mole Fe- O and 4% 4. The process of claim 1 wherein a portion of the CO- -rich stream separated in step (4) is introduced into the gas generator in step (1) as said temperature moderator.
5. The process of claim 1 wherein said hydrocarbonaceous fuel is a liquid hydrocarbon selected from the group consisting of liquefied petroleum gas; petroleum distillates and residues, gasoline, naphtha, kerosine, crude petroleum asphalt, gas oil, residual oil, tar-sand oil, shale oil, coal oil; aromatic hydrocarbons such as benzene, toluene, xylene fractions, coal tar, cycle gas oil from fluid-catalytic-cracking operation; furfural extract of coker gas oil; and mixtures thereof.
6. The process of claim 1 wherein said hydrocarbonaceous fuel is a gaseous hydrocarbon selected from the group consisting of ethane, propane, butane, pentane, refinery gas, acetylene tail gas, ethylene off-gas, and mixtures thereof.
7. A process for producing a gaseous stream comprising about 97 mole methane or more comprising 1. producing a raw process gas stream principally comprising CO, H CO and H 0, and optionally containing particulate carbon, CH H 8 and COS by partial oxidation of a hydrocarbonaceous feedstock with a free-oxygen containing gas comprising about to 99.9 mole O and optionally with a temperature moderator, in the reaction zone of a free-flow noncatalytic gas generator at an autogenous temperature in the range of about l200 to 3500F. and a pressure in the range of about 1 to 350 atm. abs.;
2. cooling, cleaning and adding supplemental H O to the effluent gas stream from l) to produce a feed gas stream having a mole ratio H O/CO in the range of about 2 to 8 for water-gas shift conversion;
3. reacting the feed gas stream from (2) in a catalytic water-gas conversion zone at a temperature in the range of about 650 to 950F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole of the CO is reacted with H O to produce H and C0 4. cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO -rich gas stream comprising at least mole CO and optionally a separate stream of H 8 and COS, thereby producing a dry hydrogen-rich gas stream comprising in mole H 52 to 93, CO 0.5 to 12, CH 44 to l, C0 0 to 6, A 0.2 to 0.4, and N 0 to 7;
5. mixing at least a portion of the CO -rich gas stream from (4) with the hydrogen-rich gas stream to provide a feed gas mixture having a mole ratio H /CO of greater than 4, and reacting substantially all of the carbon oxides insaid feed gas mixture with hydrogen at a'temperature in the range of about 400 to l500F. in a catalytic methanation zone to produce an effluent gas stream comprising at least 50 mole 7r C H 6. cooling the effluent gas stream from (5) to below the dew point. separating out condensed water. and mixing same with a second portion of said CO- -rich 5 gas stream from (4) thereby producing a feed gas stream having a mole ration H /CO of about 4:
7. reacting the feed gas stream from (6) in a second separate catalytic mcthanation zone at a temperature in the range of about 400 to 1500F. thereby m producing an effluent gas stream substantially comprising CH and H 0; and
8. cooling the effluent gas stream from (7) below the dew point. separating water therefrom. and producing said product stream comprising about 97 mole CH or more.
8. The process of claim 7 where the pressure in all steps is substantially that in the gas generator less ordinary drop in the line.
9. The process of claim 7 wherein a portion of the CO- -rich gas stream from (4) is introduced into the gas generator in l) as at least a portion of said temperature moderator.
10. The process of claim 7 wherein the catalyst in steps (5) and (7) comprises nickel oxide and aluminum oxide and the space velocity in each methanation zone is in the range of about to 10,000 standard volumes of gas per volume of catalyst per hour.
Claims (27)
1. PRODUCING A RAW PROCESS GAS STREAM PRINCIPALLY COMPRISING CO, H2, CO2, AND H2O AND OPTIONALLY CONTAINING PARTICULATE CARBON, CH4, H2S AND COS BY THE PARTIAL OXIDATION OF A HYDROCARBONACEOUS FEEDSTOCK WITH A FREEOXYGEN CONTAINING GAS COMPRISING ABOUT 90 TO 99.9 MOLE % O2 AND OPTIONALLY WITH A TEMPERATURE MODERATOR, IN THE REACTION ZONE OF A GAS GENERATOR AT AN AUTOGENOUS TEMPERATURE IN THE RANGE OF ABOUT 1200* TO 3500*F. AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 350 ATM. ABS.:
1. A PROCESS FOR PRODUCING A METHANE-RICH GAS STREAM COMPRISING
2. cooling, cleaning and adding supplemental H2O to the effluent gas stream from (1) to produce a feed gas stream for water-gas shift conversion having a mole ratio H2O/CO in the range of about 2 to 8;
2. COOLING, CLEANING AND ADDING SUPPLEMENTAL H2O TO THE EFFLUENT GAS STREAM FROM (1) TO PRODUCE A FEED GAS STREAM FOR WATER-GAS SHIFT CONVERSION HAVING A MOLE RATIO H2O/CO IN THE RANGEOF ABOUT 2 TO 8;
2. cooling, cleaning and adding supplemental H2O to the effluent gas stream from (1) to produce a feed gas stream having a mole ratio H2O/CO in the range of about 2 to 8 for water-gas shift conversion;
2. The process of claim 1 wherein the pressure in steps (2) to (6) is substantially the same as that in the gas generator in step (1) less ordinary drop in the lines.
3. The process of claim 1 where in step (3) the water-gas shift reaction takes place in contact with a sulfur resistant catalyst comprising 95 mole % Fe2O3 and 4% Cr2O3.
3. reacting the feed gas stream from (2) in a catalytic water-gas conversion zone at a temperature in the range of about 650 to 950*F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole % of the CO is reacted with H2O to produce H2 and CO2:
3. REACTING THE FEED GAS STREAM FROM (2) IN A CATALYTIC WATERGAS SHIFT CONVERSION ZONE AT A TEMPERATURE IN THE RANGE OF ABOUT 650* TO 950*F. AND A PRESSURE IN THE RANGE OF ABOUT 1 TO 350 ATM. ABS. UNTIL AT LWAST 75 MOLE % OF THE CO IS REACTED WITH H2O TO PRODUCE H2 AND CO2;
3. reacting the feed gas stream from (2) in a catalytic water-gas shift conversion zone at a temperature in the range of about 650* to 950*F. and a pressure in the range of about 1 to 350 atm. abs. until at least 75 mole % of the CO is reacted with H2O to produce H2 and CO2;
4. cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO2-rich gas stream and optionally a separate stream of H2S and COS, producing a hydrogen-rich gas stream;
4. COOLING, AND PURIFYING THE EFFLUENT GAS STREAM FROM (3) IN AN ACID-GAS PURIFICATION ZONE AND SEPARATING A CO2-RICH GAS STREAM AND OPTIONALLY A SEPARATED STREAM OF HES AND COS, PRODUCING A HYDROGEN-RICH GAS STREAM;
4. cooling, and purifying the effluent gas stream from (3) in an acid-gas purification zone and separating a CO2-rich gas stream comprising at least 95 mole % CO2 and optionally a separate stream of H2S and COS, thereby producing a dry hydrogen-rich gas stream comprising in mole %: H2 52 to 93, CO 0.5 to 12, CH4 44 to 1, CO2 0 to 6, A 0.2 to 0.4, and N2 0 to 7;
4. The process of claim 1 wherein a portion of the CO2-rich stream separated in step (4) is introduced into the gas generator in step (1) as said temperature moderator.
5. mixing at least a portion of the CO2-rich gas stream from (4) with the hydrogen-rich gas stream from (4) providing a feed gas mixture having a mole ratio H2/CO2 in the range of 4 to 10, reacting together at a temperature in the range of about 400* to 1500*F. in a catalytic methanation zone hydrogen and substantially all of the carbon oxides in said feed gas mixture, and removing from said methanation zone an effluent gas stream substantially comprising in mole % dry basis CH4 50 to 96, H2 3 to 46, CO 0 to 0.5, CO2 0.3 to 0.7, A+N2 0.2 to 8; and b. cooling the effluent gas stream from (5) and separating H2O therefrom to produce said methane-rich product stream.
5. The process of claim 1 wherein said hydrocarbonaceous fuel is a liquid hydrocarbon selected from the group consisting of liquefied petroleum gas; petroleum Distillates and residues, gasoline, naphtha, kerosine, crude petroleum asphalt, gas oil, residual oil, tar-sand oil, shale oil, coal oil; aromatic hydrocarbons such as benzene, toluene, xylene fractions, coal tar, cycle gas oil from fluid-catalytic-cracking operation; furfural extract of coker gas oil; and mixtures thereof.
5. mixing at least a portion of the CO2-rich gas stream from (4) with the hydrogen-rich gas stream to provide a feed gas mixture having a mole ratio H2/CO2 of greater than 4, and reacting substantially all of the carbon oxides in said feed gas mixture with hydrogen at a temperature in the range of about 400* to 1500*F. in a catalytic methanation zone to produce an effluent gas stream comprising at least 50 mole % CH4;
5. MIXING AT LEAST A PORTION OF THE CO2-RICH GAS STREAM FORM (4) WITH THE HYDROGEN-RICH GAS STREAM FROM (4) PROVIDING A FEED GAS MIXTURE HAVING A MOLE RATIO HE/CO2 IN THE RANGE OF 4 TO 10 REACTING TOGETHER AT A TEMPERATURE IN THE RANGE OF ABOUT 400* TO 1500*F. IN A CATALYTIC METHANATION ZONE HYDROGEN AND SUBSTANTIALLY ALL OF THE CARBON OXIDES IN SAID FEED GAS MIXTURE, AND REMOVING FROM SAID METHANATION ZONE AN EFFLUENT GAS STREAM SUBSTANTIALLY COMPRISING IN MOLE % DRY BASIS CH4 50 TO 96, H2 3 TO 46, CO 0 TO 0.5, CO2 0.3 TO 0.7, A+N2 0.2 TO 8; AND
6. COOLING THE EFFLUENT GAS STREAM FORM (5) AND SEPARATING H2O THEREFROM TO PRODUCE SAID METHANE-RICH PRODUCT STREAM.
6. cooling the effluent gas stream from (5) to below the dew point, separating out condensed water, and mixing same with a second portion of said CO2-rich gas stream from (4) thereby producing a feed gas stream having a mole ration H2/CO2 of about 4;
6. The process of claim 1 wherein said hydrocarbonaceous fuel is a gaseous hydrocarbon selected from the group consisting of ethane, propane, butane, pentane, refinery gas, acetylene tail gas, ethylene off-gas, and mixtures thereof.
7. A process for producing a gaseous stream comprising about 97 mole % methane or more comprising
7. reacting the feed gas stream from (6) in a second separate catalytic methanation zone at a temperature in the range of about 400 to 1500*F., thereby producing an effluent gas stream substantially comprising CH4 and H2O; and
8. cooling the effluent gas stream from (7) below the dew point, separating water therefrom, and producing said product stream comprising about 97 mole % CH4, or more.
8. The process of claim 7 where the pressure in all steps is substantially that in the gas generator less ordinary drop in the line.
9. The process of claim 7 wherein a portion of the CO2-rich gas stream from (4) is introduced into the gas generator in (1) as at least a portion of said temperature moderator.
10. The prOcess of claim 7 wherein the catalyst in steps (5) and (7) comprises nickel oxide and aluminum oxide and the space velocity in each methanation zone is in the range of about 100 to 10,000 standard volumes of gas per volume of catalyst per hour.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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US373533A US3890113A (en) | 1973-06-25 | 1973-06-25 | Production of methane |
JP49030703A JPS5019701A (en) | 1973-06-25 | 1974-03-19 | |
IN908/CAL/74A IN141930B (en) | 1973-06-25 | 1974-04-22 | |
BR5035/74A BR7405035D0 (en) | 1973-06-25 | 1974-06-20 | |
IT24387/74A IT1015372B (en) | 1973-06-25 | 1974-06-25 | PROCEDURE FOR PRODUCING A GASEOUS CURRENT RICH IN METHANE |
Applications Claiming Priority (1)
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US373533A US3890113A (en) | 1973-06-25 | 1973-06-25 | Production of methane |
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US3890113A true US3890113A (en) | 1975-06-17 |
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US373533A Expired - Lifetime US3890113A (en) | 1973-06-25 | 1973-06-25 | Production of methane |
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US (1) | US3890113A (en) |
JP (1) | JPS5019701A (en) |
BR (1) | BR7405035D0 (en) |
IN (1) | IN141930B (en) |
IT (1) | IT1015372B (en) |
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FR2289475A1 (en) * | 1974-10-25 | 1976-05-28 | Shell Int Research | PROCESS FOR THE PREPARATION OF HYDROCARBONS |
US3981800A (en) * | 1974-11-22 | 1976-09-21 | Era, Incorporated | High quality methane gas through modified anaerobic digestion |
FR2316319A2 (en) * | 1975-06-19 | 1977-01-28 | Rockwell International Corp | COMBUSTIBLE GAS PRODUCTION PROCESS |
US4016189A (en) * | 1974-07-27 | 1977-04-05 | Metallgesellschaft Aktiengesellschaft | Process for producing a gas which can be substituted for natural gas |
US4021366A (en) * | 1975-06-30 | 1977-05-03 | Texaco Inc. | Production of hydrogen-rich gas |
US4024171A (en) * | 1975-06-30 | 1977-05-17 | Union Oil Company Of California | Aluminum borate catalyst compositions and use thereof in chemical conversions |
US4046523A (en) * | 1974-10-07 | 1977-09-06 | Exxon Research And Engineering Company | Synthesis gas production |
US4064152A (en) * | 1975-06-16 | 1977-12-20 | Union Oil Company Of California | Thermally stable nickel-alumina catalysts useful for methanation |
US4082520A (en) * | 1975-07-18 | 1978-04-04 | Ruhrgas Aktiengesellschaft | Process of producing gases having a high calorific value |
US4113446A (en) * | 1975-07-22 | 1978-09-12 | Massachusetts Institute Of Technology | Gasification process |
US4123448A (en) * | 1977-06-01 | 1978-10-31 | Continental Oil Company | Adiabatic reactor |
US4130575A (en) * | 1974-11-06 | 1978-12-19 | Haldor Topsoe A/S | Process for preparing methane rich gases |
US4176087A (en) * | 1977-06-20 | 1979-11-27 | Conoco Methanation Company | Method for activating a hydrodesulfurization catalyst |
US4212817A (en) * | 1974-06-26 | 1980-07-15 | Linde Aktiengesellschaft | Control of highly exothermic chemical reactions |
WO1981000854A1 (en) * | 1979-09-27 | 1981-04-02 | Modar Inc | Treatment of organic material in supercritical water |
WO1981000855A1 (en) * | 1979-09-27 | 1981-04-02 | Modar Inc | Treatment of organic material in supercritical water |
US4341531A (en) * | 1980-12-08 | 1982-07-27 | Texaco Inc. | Production of methane-rich gas |
US4389283A (en) * | 1980-10-29 | 1983-06-21 | Albert Calderon | Method for making coke via induction heating |
US4436532A (en) | 1981-03-13 | 1984-03-13 | Jgc Corporation | Process for converting solid wastes to gases for use as a town gas |
US5616154A (en) * | 1992-06-05 | 1997-04-01 | Battelle Memorial Institute | Method for the catalytic conversion of organic materials into a product gas |
US5630854A (en) * | 1982-05-20 | 1997-05-20 | Battelle Memorial Institute | Method for catalytic destruction of organic materials |
US6043288A (en) * | 1998-02-13 | 2000-03-28 | Exxon Research And Engineering Co. | Gas conversion using synthesis gas produced hydrogen for catalyst rejuvenation and hydrocarbon conversion |
US6096934A (en) * | 1998-12-09 | 2000-08-01 | Uop Llc | Oxidative coupling of methane with carbon conservation |
US6103773A (en) * | 1998-01-27 | 2000-08-15 | Exxon Research And Engineering Co | Gas conversion using hydrogen produced from syngas for removing sulfur from gas well hydrocarbon liquids |
US6147126A (en) * | 1998-02-10 | 2000-11-14 | Exxon Research And Engineering Company | Gas conversion using hydrogen from syngas gas and hydroconversion tail gas |
US20020119091A1 (en) * | 1999-07-30 | 2002-08-29 | Conoco Inc. | Apparatus for recovering sulfur from H2S and concurrent production of H2 |
US20020152680A1 (en) * | 2001-04-18 | 2002-10-24 | Callaghan Vincent M. | Fuel cell power plant |
US20070130832A1 (en) * | 2005-12-13 | 2007-06-14 | General Electric Company | Methods and apparatus for converting a fuel source to hydrogen |
US20070299288A1 (en) * | 2004-02-12 | 2007-12-27 | Paul Scherrer Institut | Process for the Synthetic Generation of Methane |
US20090247653A1 (en) * | 2006-04-06 | 2009-10-01 | Fluor Technologies Corporation | Configurations And Methods of SNG Production |
WO2009124666A2 (en) * | 2008-04-08 | 2009-10-15 | Linde Aktiengesellschaft | Method and device for producing hydrogen and/or carbon monoxide from coke |
US20100272619A1 (en) * | 2009-04-22 | 2010-10-28 | General Electric Company | Method and apparatus for substitute natural gas generation |
CN101880558A (en) * | 2009-05-07 | 2010-11-10 | 赫多特普索化工设备公司 | Alternative Natural Gas Production Methods |
ITMI20091211A1 (en) * | 2009-07-08 | 2011-01-09 | Foster Wheeler Italiana | SYNTHESIS GAS METHANATION PROCESS AND PLANT |
WO2012064936A1 (en) * | 2010-11-10 | 2012-05-18 | Air Products And Chemicals, Inc. | Syngas produced by plasma gasification |
CN102911739A (en) * | 2012-11-16 | 2013-02-06 | 华东理工大学 | Method for preparing synthesis gas by coupling fixed bed gasification and non-catalytic partial oxidation |
KR101268774B1 (en) | 2010-12-28 | 2013-05-29 | 주식회사 포스코 | Synthetic natural gas production process enhanced reaction efficiency |
US8980204B2 (en) | 2010-05-24 | 2015-03-17 | Air Products And Chemicals, Inc. | Process and system for syngas treatment |
US9012523B2 (en) | 2011-12-22 | 2015-04-21 | Kellogg Brown & Root Llc | Methanation of a syngas |
US20150110691A1 (en) * | 2010-02-13 | 2015-04-23 | Mcalister Technologies, Llc | Liquid fuel for isolating waste material and storing energy |
US9540578B2 (en) | 2010-02-13 | 2017-01-10 | Mcalister Technologies, Llc | Engineered fuel storage, respeciation and transport |
CN107011950A (en) * | 2016-01-28 | 2017-08-04 | 惠生工程(中国)有限公司 | A kind of method for gas purification for coal base synthesis of natural device of air |
EP2906666B1 (en) | 2012-10-11 | 2018-06-20 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg | Process and system for producing a methane-containing natural gas substitute |
CN109111968A (en) * | 2018-09-06 | 2019-01-01 | 鄂尔多斯应用技术学院 | A kind of method that coke-stove gas prepares liquefied natural gas |
CN109609203A (en) * | 2019-01-09 | 2019-04-12 | 中海石油气电集团有限责任公司 | A kind of method of coal coproduction natural gas and hydrogen |
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BR112015014440A2 (en) * | 2012-12-20 | 2017-07-11 | Solvay | process for producing a purified aqueous hydrogen peroxide solution |
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- 1974-04-22 IN IN908/CAL/74A patent/IN141930B/en unknown
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Cited By (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4212817A (en) * | 1974-06-26 | 1980-07-15 | Linde Aktiengesellschaft | Control of highly exothermic chemical reactions |
US4016189A (en) * | 1974-07-27 | 1977-04-05 | Metallgesellschaft Aktiengesellschaft | Process for producing a gas which can be substituted for natural gas |
US4046523A (en) * | 1974-10-07 | 1977-09-06 | Exxon Research And Engineering Company | Synthesis gas production |
FR2289475A1 (en) * | 1974-10-25 | 1976-05-28 | Shell Int Research | PROCESS FOR THE PREPARATION OF HYDROCARBONS |
US4130575A (en) * | 1974-11-06 | 1978-12-19 | Haldor Topsoe A/S | Process for preparing methane rich gases |
US3981800A (en) * | 1974-11-22 | 1976-09-21 | Era, Incorporated | High quality methane gas through modified anaerobic digestion |
US4064152A (en) * | 1975-06-16 | 1977-12-20 | Union Oil Company Of California | Thermally stable nickel-alumina catalysts useful for methanation |
US4017271A (en) * | 1975-06-19 | 1977-04-12 | Rockwell International Corporation | Process for production of synthesis gas |
FR2316319A2 (en) * | 1975-06-19 | 1977-01-28 | Rockwell International Corp | COMBUSTIBLE GAS PRODUCTION PROCESS |
US4021366A (en) * | 1975-06-30 | 1977-05-03 | Texaco Inc. | Production of hydrogen-rich gas |
US4024171A (en) * | 1975-06-30 | 1977-05-17 | Union Oil Company Of California | Aluminum borate catalyst compositions and use thereof in chemical conversions |
US4082520A (en) * | 1975-07-18 | 1978-04-04 | Ruhrgas Aktiengesellschaft | Process of producing gases having a high calorific value |
US4113446A (en) * | 1975-07-22 | 1978-09-12 | Massachusetts Institute Of Technology | Gasification process |
US4123448A (en) * | 1977-06-01 | 1978-10-31 | Continental Oil Company | Adiabatic reactor |
US4176087A (en) * | 1977-06-20 | 1979-11-27 | Conoco Methanation Company | Method for activating a hydrodesulfurization catalyst |
WO1981000854A1 (en) * | 1979-09-27 | 1981-04-02 | Modar Inc | Treatment of organic material in supercritical water |
WO1981000855A1 (en) * | 1979-09-27 | 1981-04-02 | Modar Inc | Treatment of organic material in supercritical water |
US4389283A (en) * | 1980-10-29 | 1983-06-21 | Albert Calderon | Method for making coke via induction heating |
US4341531A (en) * | 1980-12-08 | 1982-07-27 | Texaco Inc. | Production of methane-rich gas |
US4436532A (en) | 1981-03-13 | 1984-03-13 | Jgc Corporation | Process for converting solid wastes to gases for use as a town gas |
US5630854A (en) * | 1982-05-20 | 1997-05-20 | Battelle Memorial Institute | Method for catalytic destruction of organic materials |
US5616154A (en) * | 1992-06-05 | 1997-04-01 | Battelle Memorial Institute | Method for the catalytic conversion of organic materials into a product gas |
US6103773A (en) * | 1998-01-27 | 2000-08-15 | Exxon Research And Engineering Co | Gas conversion using hydrogen produced from syngas for removing sulfur from gas well hydrocarbon liquids |
US6147126A (en) * | 1998-02-10 | 2000-11-14 | Exxon Research And Engineering Company | Gas conversion using hydrogen from syngas gas and hydroconversion tail gas |
US6043288A (en) * | 1998-02-13 | 2000-03-28 | Exxon Research And Engineering Co. | Gas conversion using synthesis gas produced hydrogen for catalyst rejuvenation and hydrocarbon conversion |
USRE38170E1 (en) * | 1998-02-13 | 2003-07-01 | Exxonmobil Research And Engineering Company | Gas conversion using synthesis gas produced hydrogen for catalyst rejuvenation and hydrocarbon conversion |
US6096934A (en) * | 1998-12-09 | 2000-08-01 | Uop Llc | Oxidative coupling of methane with carbon conservation |
US20020119091A1 (en) * | 1999-07-30 | 2002-08-29 | Conoco Inc. | Apparatus for recovering sulfur from H2S and concurrent production of H2 |
US20020152680A1 (en) * | 2001-04-18 | 2002-10-24 | Callaghan Vincent M. | Fuel cell power plant |
US8313544B2 (en) * | 2004-02-12 | 2012-11-20 | Paul Scherrer Institut | Process for the synthetic generation of methane |
US20070299288A1 (en) * | 2004-02-12 | 2007-12-27 | Paul Scherrer Institut | Process for the Synthetic Generation of Methane |
WO2007070470A3 (en) * | 2005-12-13 | 2007-08-02 | Gen Electric | Methods and apparatus for converting a fuel source to hydrogen |
US20070130832A1 (en) * | 2005-12-13 | 2007-06-14 | General Electric Company | Methods and apparatus for converting a fuel source to hydrogen |
WO2007070470A2 (en) * | 2005-12-13 | 2007-06-21 | General Electric Company | Methods and apparatus for converting a fuel source to hydrogen |
US20090247653A1 (en) * | 2006-04-06 | 2009-10-01 | Fluor Technologies Corporation | Configurations And Methods of SNG Production |
WO2009124666A2 (en) * | 2008-04-08 | 2009-10-15 | Linde Aktiengesellschaft | Method and device for producing hydrogen and/or carbon monoxide from coke |
WO2009124666A3 (en) * | 2008-04-08 | 2010-04-01 | Linde Aktiengesellschaft | Method and device for producing hydrogen and/or carbon monoxide from coke |
AU2010201534B2 (en) * | 2009-04-22 | 2016-04-14 | Air Products And Chemicals, Inc. | Method and apparatus for substitute natural gas generation |
US20100272619A1 (en) * | 2009-04-22 | 2010-10-28 | General Electric Company | Method and apparatus for substitute natural gas generation |
US8182771B2 (en) * | 2009-04-22 | 2012-05-22 | General Electric Company | Method and apparatus for substitute natural gas generation |
US20100286292A1 (en) * | 2009-05-07 | 2010-11-11 | Christian Wix | Process for the production of substitute natural gas |
KR20100121423A (en) * | 2009-05-07 | 2010-11-17 | 할도르 토프쉐 에이/에스 | Process for production of substitute natural gas |
EP2261308A1 (en) * | 2009-05-07 | 2010-12-15 | Haldor Topsøe A/S | Process for the production of natural gas |
CN101880558A (en) * | 2009-05-07 | 2010-11-10 | 赫多特普索化工设备公司 | Alternative Natural Gas Production Methods |
US8530529B2 (en) | 2009-05-07 | 2013-09-10 | Haldor Topsoe A/S | Process for the production of substitute natural gas |
CN101880558B (en) * | 2009-05-07 | 2013-08-14 | 赫多特普索化工设备公司 | Process for the production of substitute natural gas |
AU2010269949B2 (en) * | 2009-07-08 | 2016-02-04 | Wood Italiana S.r.l. | Synthesis gas methanation process and apparatus |
US8975303B2 (en) | 2009-07-08 | 2015-03-10 | Foster Wheeler Italiana S.R.L. | Synthesis gas methanation process and apparatus |
ITMI20091211A1 (en) * | 2009-07-08 | 2011-01-09 | Foster Wheeler Italiana | SYNTHESIS GAS METHANATION PROCESS AND PLANT |
CN102597172A (en) * | 2009-07-08 | 2012-07-18 | 福斯特惠勒意大利有限责任公司 | Synthesis gas methanation process and apparatus |
WO2011004251A1 (en) * | 2009-07-08 | 2011-01-13 | Foster Wheeler Italiana S.R.L. | Synthesis gas methanation process and apparatus |
CN102597172B (en) * | 2009-07-08 | 2014-12-31 | 福斯特惠勒意大利有限责任公司 | Synthesis gas methanation process and apparatus |
US20150110691A1 (en) * | 2010-02-13 | 2015-04-23 | Mcalister Technologies, Llc | Liquid fuel for isolating waste material and storing energy |
US9540578B2 (en) | 2010-02-13 | 2017-01-10 | Mcalister Technologies, Llc | Engineered fuel storage, respeciation and transport |
US8980204B2 (en) | 2010-05-24 | 2015-03-17 | Air Products And Chemicals, Inc. | Process and system for syngas treatment |
WO2012064936A1 (en) * | 2010-11-10 | 2012-05-18 | Air Products And Chemicals, Inc. | Syngas produced by plasma gasification |
KR101268774B1 (en) | 2010-12-28 | 2013-05-29 | 주식회사 포스코 | Synthetic natural gas production process enhanced reaction efficiency |
US9012523B2 (en) | 2011-12-22 | 2015-04-21 | Kellogg Brown & Root Llc | Methanation of a syngas |
EP2906666B1 (en) | 2012-10-11 | 2018-06-20 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg | Process and system for producing a methane-containing natural gas substitute |
CN102911739A (en) * | 2012-11-16 | 2013-02-06 | 华东理工大学 | Method for preparing synthesis gas by coupling fixed bed gasification and non-catalytic partial oxidation |
CN107011950A (en) * | 2016-01-28 | 2017-08-04 | 惠生工程(中国)有限公司 | A kind of method for gas purification for coal base synthesis of natural device of air |
CN107011950B (en) * | 2016-01-28 | 2019-12-27 | 惠生工程(中国)有限公司 | Gas purification method for coal-based natural gas synthesis device |
CN109111968A (en) * | 2018-09-06 | 2019-01-01 | 鄂尔多斯应用技术学院 | A kind of method that coke-stove gas prepares liquefied natural gas |
CN109609203A (en) * | 2019-01-09 | 2019-04-12 | 中海石油气电集团有限责任公司 | A kind of method of coal coproduction natural gas and hydrogen |
Also Published As
Publication number | Publication date |
---|---|
IN141930B (en) | 1977-05-07 |
BR7405035D0 (en) | 1975-01-21 |
IT1015372B (en) | 1977-05-10 |
JPS5019701A (en) | 1975-03-01 |
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